JP2019034544A - Laminate, molded article, and in-tank tube - Google Patents

Abstract

To provide a laminate high in retention rate of elasticity modulus even at a high temperature, and having proper hardness, and an in-tank tube formed from the laminate.SOLUTION: There is provided a laminate containing a layer (A) consisting of a fluorine resin and a layer (B) consisting of a polyamide resin, in which the fluorine resin is a copolymer containing a copolymerization unit of tetrafluoroethylene and a copolymerization unit of vinylidene fluoride, and storage elastic modulus (E') at 170°C by a dynamic viscoelasticity measurement is 60 to 400 MPa.SELECTED DRAWING: Figure 1

Description

The present invention relates to a laminate, a molded article, and an in-tank tube.

In general, the fuel piping system of an automobile has a mechanism for sucking up and supplying the fuel necessary for operating the engine from the inside of the fuel tank. The fuel is sucked up by a pump installed in the fuel tank. Has been done. A hose connected to the fuel pump in the fuel tank is called an in-tank tube.

For example, Patent Document 1 describes an in-tank tube for automobile fuel that is formed in a single-layer structure made of a resin material containing an aliphatic polyamide resin as a main component and that has specific pressure resistance characteristics.

International Publication No. 2011-114865

In automobile fuel piping systems and the like, the members used for piping and the like become high temperature, and for in-tank tube applications, a laminate having a high elastic modulus retention rate and moderate hardness even at high temperatures. desired. However, the in-tank tube described in Patent Document 1 has room for improvement in terms of the elastic modulus retention at high temperatures.

The present invention provides a laminate having a high elastic modulus retention rate and moderate hardness even at high temperatures. In addition, an in-tank tube having a high elastic modulus retention rate and moderate hardness even at high temperatures is provided.

The present invention is a laminate comprising a layer (A) made of a fluororesin and a layer (B) made of a polyamide resin, wherein the fluororesin comprises a copolymer unit of tetrafluoroethylene and a copolymer unit of vinylidene fluoride. And a storage elastic modulus (E ′) at 170 ° C. by dynamic viscoelasticity measurement of 60 to 400 MPa.

The polyamide resin preferably has a melting point of 200 ° C. or higher.

The present invention is also a molded article formed from the laminate. The present invention is also an in-tank tube formed from the laminate (hereinafter also referred to as “first in-tank tube of the present invention”). The in-tank tube is preferably disposed in the fuel tank.

The present invention is an in-tank tube including a layer (A ′) made of a fluororesin, wherein the fluororesin is a copolymer including a polymer unit based on tetrafluoroethylene and a polymer unit based on vinylidene fluoride, And it is also an in-tank tube whose storage elastic modulus (E ') in 170 degreeC by dynamic viscoelasticity measurement is 60-400 Mpa (henceforth "the 2nd in-tank tube of this invention"). The in-tank tube is preferably disposed in the fuel tank.

The second in-tank tube of the present invention is also preferably composed of only a layer (A ′) made of a fluororesin. The in-tank tube is preferably disposed in the fuel tank.

The fluororesin preferably has a tensile elastic modulus at 150 ° C. of 15% or more compared to the tensile elastic modulus at room temperature.

In the laminate and the in-tank tube of the present invention, the fluororesin is represented by tetrafluoroethylene, vinylidene fluoride, an ethylenically unsaturated monomer represented by the formula (1) and / or the formula (2). It is preferable that it is a copolymer containing a copolymer unit with the ethylenically unsaturated monomer.
Formula (1): CX ¹ X ² = CX ³ (CF ₂ ) _n X ⁴
(Wherein X ¹ , X ² , X ³ and X ⁴ are the same or different and represent H, F or Cl, and n represents an integer of 0 to 8, except for tetrafluoroethylene and vinylidene fluoride. )
Formula (2): CF ₂ = CF-ORf ¹
(In the formula, Rf ¹ represents an alkyl group having 1 to 3 carbon atoms or a fluoroalkyl group.)

By including a fluororesin layer and a polyamide resin layer made of a specific fluororesin, the laminate of the present invention has a high elastic modulus retention rate and an appropriate hardness even at high temperatures. The first in-tank tube of the present invention formed from the laminate includes a fluororesin layer made of a specific fluororesin and a polyamide resin layer, so that the elastic modulus retention rate is high even at high temperatures and is moderate. Has a good hardness.
Since the second in-tank tube of the present invention includes a fluororesin layer made of a specific fluororesin, it has a high elastic modulus retention even at high temperatures and has an appropriate hardness.

It is a schematic diagram which shows the inside of the fuel tank of a motor vehicle.

(A) Fluororesin layer The layer (A) is formed from a fluororesin. The fluororesin is a copolymer containing a copolymerized unit of tetrafluoroethylene and a copolymerized unit of vinylidene fluoride, and a storage elastic modulus (E ′) at 170 ° C. by dynamic viscoelasticity measurement is 60 to 400 MPa.

The fluororesin has a storage elastic modulus (E ′) at 170 ° C. of 60 to 400 MPa as measured by dynamic viscoelasticity. The storage elastic modulus is a value measured at 170 ° C. by dynamic viscoelasticity measurement. More specifically, the storage elastic modulus is a dynamic viscoelastic device DVA220 manufactured by IT-Measurement Control Co., Ltd., having a length of 30 mm, a width of 5 mm, and a thickness of 0. This is a value obtained by measuring a 25 mm sample under the conditions of a tensile mode, a grip width of 20 mm, a measurement temperature of 25 ° C. to 250 ° C., a temperature increase rate of 2 ° C./min, and a frequency of 1 Hz. A preferable storage elastic modulus (E ′) at 170 ° C. is 80 to 350 MPa, and a more preferable storage elastic modulus (E ′) is 100 to 350 MPa.

The fluororesin is a copolymer composed only of copolymerized units of tetrafluoroethylene and vinylidene fluoride, or tetrafluoroethylene, vinylidene fluoride and ethylenically unsaturated monomer (however, tetrafluoroethylene and vinylidene fluoride). A copolymer containing copolymerized units (excluding ride).

The ethylenically unsaturated monomer is not particularly limited as long as it is a monomer copolymerizable with tetrafluoroethylene and vinylidene fluoride, but is ethylenic represented by the following formulas (1) and (2). It is preferably at least one unsaturated monomer.

Formula (1): CX ¹ X ² = CX ³ (CF ₂ ) _n X ⁴
(Wherein X ¹ , X ² , X ³ and X ⁴ are the same or different and represent H, F or Cl, and n represents an integer of 0 to 8, except for tetrafluoroethylene and vinylidene fluoride. )

Formula (2): CF ₂ = CF-ORf ¹
(In the formula, Rf ¹ represents an alkyl group having 1 to 3 carbon atoms or a fluoroalkyl group.)

Examples of the ethylenically unsaturated monomer represented by the formula (1) include CF ₂ = CFCl, CF ₂ = CFCF ₃ , and the following formula (3)
^{_{CH 2 = CF- (CF 2)}} n X 4 (3)
(Wherein X ⁴ and n are the same as above) and the following formula (4)
^{_{CH 2 = CH- (CF 2)}} n X 4 (4)
(Wherein X ⁴ and n are the same as above)
It is preferably at least one selected from the group consisting of: CF ₂ = CFCl, CH ₂ = CFCF ₃ , CH ₂ = CH-C ₄ F ₉ , CH ₂ = CH-C ₆ F ₁₃ , CH ₂ = _CF-C 3, more preferably _{F 6} is H and _CF 2 = CFCF _3, at least one selected from the group consisting _of, CF 2 = CFCl and _CH 2 = CFCF _3, at least one selected from the group consisting of More preferably.

The ethylenically unsaturated monomer represented by the formula (2) includes a group consisting of CF ₂ = CF-OCF ₃ , CF ₂ = CF-OCF ₂ CF ₃ and CF ₂ = CF-OCF ₂ CF ₂ CF _3. It is preferable that it is at least one selected from more.

The fluororesin is
58.0-85.0 mol% tetrafluoroethylene,
10.0-41.9 mol% vinylidene fluoride, and
0.1-5.0 mol% of ethylenically unsaturated monomer represented by formula (1) CX ¹ X ² = CX ³ (CF ₂ ) _n X ⁴ (1)
(Wherein X ¹ , X ² , X ³ and X ⁴ are the same or different and represent H, F or Cl, and n represents an integer of 0 to 8, except for tetrafluoroethylene and vinylidene fluoride. )
It is preferable that it is a copolymer containing the copolymerization unit of the ethylenically unsaturated monomer represented by these.

More preferably,
58.0-85.0 mol% tetrafluoroethylene,
12.0-41.9 mol% vinylidene fluoride, and
0.1 to 3.0 mol% of an ethylenically unsaturated monomer represented by the formula (1),
It is a copolymer containing the copolymerization unit.

The fluororesin is
55.0-90.0 mol% tetrafluoroethylene,
9.2-44.2 mol% vinylidene fluoride, and
0.1 to 0.8 mol% of formula (2):
CF ₂ = CF-ORf ¹ (2)
(In the formula, Rf ¹ represents an alkyl group having 1 to 3 carbon atoms or a fluoroalkyl group.)
It is also preferable that it is a copolymer containing the copolymerization unit of the ethylenically unsaturated monomer represented by these.

More preferably,
58.0-85.0 mol% tetrafluoroethylene,
14.5 to 41.9 mol% vinylidene fluoride, and
0.1 to 0.5 mol% of an ethylenically unsaturated monomer represented by the formula (2),
It is a copolymer containing the copolymerization unit.

The fluororesin is 55.0-90.0 mol% tetrafluoroethylene,
6.2-44.8 mol% vinylidene fluoride,
0.1 to 3.0 mol% of an ethylenically unsaturated monomer represented by the formula (1), and
It is also preferable that it is a copolymer containing a copolymer unit of 0.1 to 0.8 mol% of an ethylenically unsaturated monomer represented by the formula (2).

More preferably,
58.0-85.0 mol% tetrafluoroethylene,
11.5-39.8 mol% vinylidene fluoride,
0.1 to 3.0 mol% of an ethylenically unsaturated monomer represented by the formula (1), and
0.1 to 0.5 mol% of an ethylenically unsaturated monomer represented by the formula (2),
It is a copolymer containing the copolymerization unit.

When the content of each monomer is within the above-mentioned range, the fluororesin has higher crystallinity than a conventionally known copolymer composed of tetrafluoroethylene, vinylidene fluoride, and a third component, and is heated to a high temperature. However, the elastic modulus retention is high.
Further, the conventional tetrafluoroethylene and vinylidene fluoride binary copolymer not containing the third component and having a tetrafluoroethylene content of more than 50 mol% is remarkably inferior in the crack resistance of the molded product. The above copolymer is excellent in crack resistance.

The content of each copolymer unit in the copolymer can be calculated by appropriately combining NMR and elemental analysis depending on the type of monomer.
The fluororesin used in the present invention has high crystallinity by copolymerizing tetrafluoroethylene, vinylidene fluoride, and an ethylenically unsaturated monomer at a specific composition ratio. Therefore, the laminate of the present invention including the layer (A) made of this fluororesin has excellent barrier properties and has a high elastic modulus retention even at high temperatures.
The fluororesin preferably has a tensile elastic modulus at 150 ° C. of 15% or more compared to the tensile elastic modulus at room temperature (25 ° C.), more preferably 20% or more. % Or more is particularly preferable.
The fluororesin preferably has a tensile elastic modulus at 150 ° C. of 40% or more compared to the tensile elastic modulus at 100 ° C., more preferably 60% or more, and 70% It is more preferable to hold more than 80%, and it is particularly preferable to hold 80% or more. Thus, the high retention rate of the tensile elastic modulus at a high temperature enables the laminate to retain its hardness even at a high temperature, and can be used without bending due to vibration, pulsation, internal pressure, etc. during use.
The tensile elastic modulus is a value measured at a tensile speed of 100 mm / min using a micro dumbbell having a thickness of 2 mm in accordance with ASTM D1708. The results are average values carried out with N = 5.
The retention rate of the tensile elastic modulus is particularly preferable when used as an in-tank tube.

The fluororesin preferably has a melt flow rate (MFR) of 0.1 to 50 g / 10 minutes.

The above MFR is based on ASTM D3307-01 and uses a melt indexer (manufactured by Toyo Seiki Co., Ltd.) at 297 ° C. under a load of 5 kg and the mass of the polymer flowing out from a nozzle having an inner diameter of 2 mm and a length of 8 mm per 10 minutes. (G / 10 minutes).

The fluororesin preferably has a melting point of 180 ° C. or higher, and the upper limit may be 290 ° C. A more preferred lower limit is 200 ° C and an upper limit is 270 ° C.

The melting point is measured using a differential scanning calorimeter RDC220 (manufactured by Seiko Instruments) at a heating rate of 10 ° C./min according to ASTM D-4591, and the temperature corresponding to the peak of the endothermic curve obtained is the melting point. And

The fluororesin preferably has a thermal decomposition starting temperature of 360 ° C. or higher. A more preferred lower limit is 370 ° C. If the said thermal decomposition start temperature is in the said range, an upper limit can be made into 450 degreeC, for example.

The thermal decomposition start temperature is a temperature at which 1% by mass of the fluororesin subjected to the heating test is decomposed, and the mass of the fluororesin subjected to the heating test using the differential thermal / thermogravimetric measuring device [TG-DTA] is This is a value obtained by measuring the temperature when the mass decreases by 1% by mass.

The fluororesin can be produced by a polymerization method such as solution polymerization, bulk polymerization, emulsion polymerization, suspension polymerization, etc., but is manufactured by emulsion polymerization or suspension polymerization in that it is industrially easy to implement. Is preferred.

In the above polymerization, a polymerization initiator, a surfactant, a chain transfer agent, and a solvent can be used, and conventionally known ones can be used.

As said polymerization initiator, an oil-soluble radical polymerization initiator or a water-soluble radical initiator can be used.

The oil-soluble radical polymerization initiator may be a known oil-soluble peroxide, for example, dialkyl such as diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, disec-butyl peroxydicarbonate, etc. Peroxyesters such as peroxycarbonates, t-butylperoxyisobutyrate and t-butylperoxypivalate, and dialkyl peroxides such as di-t-butylperoxide are also used as di (ω-hydro -Dodecafluoroheptanoyl) peroxide, di (ω-hydro-tetradecafluoroheptanoyl) peroxide, di (ω-hydro-hexadecafluorononanoyl) peroxide, di (perfluorobutyryl) peroxide, di (Pafuru Oroba Reriru) -Oxide, di (perfluorohexanoyl) peroxide, di (perfluoroheptanoyl) peroxide, di (perfluorooctanoyl) peroxide, di (perfluorononanoyl) peroxide, di (ω-chloro-hexafluoro) Butyryl) peroxide, di (ω-chloro-decafluorohexanoyl) peroxide, di (ω-chloro-tetradecafluorooctanoyl) peroxide, ω-hydro-dodecafluoroheptanoyl-ω-hydrohexadecafluoro Nonanoyl-peroxide, ω-chloro-hexafluorobutyryl-ω-chloro-decafluorohexanoyl-peroxide, ω-hydrododecafluoroheptanoyl-perfluorobutyryl-peroxide, di (dichloropentafluorobuta Yl) peroxide, di (trichlorooctafluorohexanoyl) peroxide, di (tetrachloroundecafluorooctanoyl) peroxide, di (pentachlorotetradecafluorodecanoyl) peroxide, di (undecachlorodotria contourer) Fluorodocosanoyl) peroxide di [perfluoro (or fluorochloro) acyl] peroxides and the like are typical examples.

The water-soluble radical polymerization initiator may be a known water-soluble peroxide, for example, ammonium salts such as persulfuric acid, perboric acid, perchloric acid, perphosphoric acid, percarbonate, potassium salts, sodium salts , T-butyl permaleate, t-butyl hydroperoxide and the like. A reducing agent such as sulfites and sulfites may be used in combination with the peroxide, and the amount used may be 0.1 to 20 times the peroxide.

As the surfactant, a known surfactant can be used. For example, a nonionic surfactant, an anionic surfactant, a cationic surfactant, or the like can be used. Among these, fluorine-containing anionic surfactants are preferable, and may include ether-bonded oxygen (that is, oxygen atoms may be inserted between carbon atoms), linear or branched having 4 to 20 carbon atoms. A fluorine-containing anionic surfactant is more preferable. The addition amount (with respect to polymerization water) is preferably 50 to 5000 ppm.

Examples of the chain transfer agent include hydrocarbons such as ethane, isopentane, n-hexane and cyclohexane; aromatics such as toluene and xylene; ketones such as acetone; acetates such as ethyl acetate and butyl acetate; Examples include alcohols such as methanol and ethanol; mercaptans such as methyl mercaptan; halogenated hydrocarbons such as carbon tetrachloride, chloroform, methylene chloride, and methyl chloride. The addition amount may vary depending on the chain transfer constant of the compound used, but is usually used in the range of 0.01 to 20% by mass with respect to the polymerization solvent.

Examples of the solvent include water, a mixed solvent of water and alcohol, and the like.

In the suspension polymerization, a fluorine-based solvent may be used in addition to water. Examples of the fluorine-based solvent include hydrochlorofluoroalkanes such as CH ₃ CClF ₂ , CH ₃ CCl ₂ F, CF ₃ CF ₂ CCl ₂ H, CF ₂ ClCF ₂ CFHCl; CF ₂ ClCFClCF ₂ CF ₃ , CF ₃ CFClCFClCF _3, etc. Perfluoroalkanes such as perfluorocyclobutane, CF ₃ CF ₂ CF ₂ CF ₃ , CF ₃ CF ₂ CF ₂ CF ₂ CF ₃ , CF ₃ CF ₂ CF ₂ CF ₂ CF ₂ CF ₃ , etc. Among them, perfluoroalkanes are preferable. The amount of the fluorine-based solvent used is preferably 10 to 100% by mass with respect to the aqueous medium from the viewpoint of suspendability and economy.

It does not specifically limit as polymerization temperature, It may be 0-100 degreeC. The polymerization pressure is appropriately determined according to other polymerization conditions such as the type, amount and vapor pressure of the solvent to be used, the polymerization temperature, etc., but may usually be 0 to 9.8 MPaG.

(B) Layer Made of Polyamide Resin The polyamide resin is a polymer having an amide bond [—NH—C (═O) —] as a repeating unit in the molecule.
The polyamide resin is a so-called nylon made of a polymer in which an amide bond in a molecule is bonded to an aliphatic structure or an alicyclic structure, or a polymer in which an amide bond in a molecule is bonded to an aromatic structure. Any of so-called aramids may be used.

The nylon is not particularly limited. For example, nylon 6, nylon 66, nylon 11, nylon 12, nylon 610, nylon 612, nylon 6/66, nylon 66/12, nylon 1010, nylon 46, nylon 6T, nylon 9T , Nylon 10T, metaxylylenediamine / adipic acid copolymer, and the like, and two or more of these may be used in combination.
The aramid is not particularly limited, and examples thereof include polyparaphenylene terephthalamide and polymetaphenylene isophthalamide.

The polyamide resin is selected from the group consisting of nylon 6, nylon 66, nylon 11, nylon 12, nylon 610, nylon 612, nylon 6T, nylon 9T, nylon 6/66, nylon 66/12, and nylon 1010. And at least one selected from the group consisting of nylon 610, nylon 612, nylon 1010, nylon 6 and nylon 66 is more preferable. Two or more of these may be used in combination.

The melting point of the polyamide resin is preferably 130 ° C. or higher. If the melting point is lower than 130 ° C, the polyamide may be melted in the use environment. The melting point of the polyamide resin is more preferably 150 ° C. or higher, further preferably 180 ° C. or higher, and particularly preferably 200 ° C. or higher.
Although the upper limit of melting | fusing point is not specifically limited, For example, from a viewpoint of the adhesiveness of a layer (A) and a layer (B), it is preferable that melting | fusing point of a polyamide resin is 260 degrees C or less, and is 240 degrees C or less. More preferred. In the present specification, the melting point is a value obtained by measuring with a differential scanning calorimeter [DSC].

Although the weight average molecular weight of the said polyamide resin is not specifically limited, For example, it is preferable that it is 1000-1 million. More preferably, it is 5000-500000, More preferably, it is 10000-300000.
The weight average molecular weight is a value obtained by measurement by gel permeation chromatography measurement.

Each layer constituting the laminate of the present invention includes polymers such as polyethylene, polypropylene, polyester, polyurethane, calcium carbonate, talc, celite, clay, titanium oxide, carbon black, barium sulfate and other inorganic fillers, pigments, flame retardants, Lubricants, light stabilizers, weathering stabilizers, antistatic agents, ultraviolet absorbers, antioxidants, mold release agents, foaming agents, fragrances, oils, softening agents, etc., as long as they do not affect the effects of the present invention. You may contain.

The laminate of the present invention includes a layer (A) made of the fluororesin and a layer (B) made of a polyamide resin, so that it has an appropriate hardness and has a high elastic modulus retention even at high temperatures. Can be used without sagging even at high temperatures. It also has excellent fuel resistance and low fuel permeability.

In the laminate of the present invention, the layer (A) may have a thickness of 0.01 to 2.0 mm, preferably 0.05 to 1.0 mm, and the layer (B) has a thickness of 0.1 to 4.0 mm. Preferably, it is 0.2-2.0 mm.
Since the laminated body of this invention has the layer (B) which consists of a polyamide resin, even if it is a case where a layer (A) is thin as mentioned above, the laminated body of moderate hardness is obtained.

The configuration of the laminate is not particularly limited, and for example, a two-layer configuration composed of a layer (A) and a layer (B), or a layer (A) inserted between two types of the same or different layers (B). A three-layer structure, a three-layer structure in which a layer (B) is inserted between two types of the same or different layers (A), and the like can be used. Among them, the configuration of layer (A) / layer (B) / layer (A) having a fluororesin layer in the inner layer and the outer layer is particularly preferable. An arbitrary material can be further laminated on the laminate of the present invention.

The method for producing the laminate of the present invention is not particularly limited, and after forming each layer, both layers may be laminated and bonded to obtain a laminate, or after forming one layer, Another layer may be formed on that layer to obtain a laminate.

For example, a layer (A) and a layer (B) may be formed, and both layers may be laminated and bonded by hot pressing to obtain a laminate, or after one layer is formed, A laminate may be obtained by melt extrusion, or two layers may be simultaneously formed and laminated by coextrusion.
The hot pressing or extrusion may be appropriately performed by a known method according to the material to be used.
In addition, also when it is set as the laminated structure of three or more layers, it can manufacture by coextrusion molding etc. similarly.

For example, (1) a method in which the layers constituting the laminate are coextruded in a molten state to thermally bond the layers (melt adhesion) to form the laminate in one step (coextrusion molding), (2) extrusion (3) A method of forming a laminated body by extruding a molten resin with an extruder on the surface of a layer prepared in advance, (4) ) After electrostatically coating the polymer constituting the layer that will be adjacent to the layer on the surface of the layer prepared in advance, the coating is obtained by heating from the whole or the coated side. A laminate can be formed by a method in which the polymer subjected to 1 is heated and melted to form a layer.

From the viewpoint of bonding the layer (A) and the layer (B) more firmly, a coextrusion molding method is preferable.
In the above-mentioned coextrusion molding method, the melt of the resin for forming each layer that is kneaded and melted in two or more extruders equipped with screws and exits from the discharge port is brought into contact with the melted state while the tip of the extruder It will be extruded through a die placed on and will be formed into a laminate.

In the coextrusion molding method, the cylinder temperature is preferably 150 to 400 ° C, and the die temperature is more preferably 200 to 400 ° C. Moreover, although the rotation speed of a screw can be set suitably, it is preferable that it is 5-200 rpm, and, as for the residence time in the extruder of a melt, 1-20 minutes are preferable.

In the laminate of the present invention, the adhesive strength between the fluororesin layer (A) and the polyamide resin layer (B) is preferably 1 N / cm or more as the peel strength between the two layers, and preferably 2 N / cm or more. Is more preferable.
For the peel strength, a 1 cm wide test piece was cut from the tube, a 180 ° peel test was performed at a speed of 25 mm / min with a Tensilon universal tester, and the average of the five maximum points in the elongation-tensile strength graph was bonded between the layers. This is the value obtained as the strength.

The laminate of the present invention can be suitably used when using a biodiesel fuel whose use environment is high. Biodiesel fuel refers to a fuel containing FAME obtained by subjecting vegetable oil to transesterification with methanol and decomposing and removing glycerin. Examples of FAME include RME derived from rapeseed oil, SME derived from soybean, SFME derived from sunflower oil, PME derived from palm oil, mixed fatty acid methyl ester containing unsaturated fatty acid methyl ester such as JME derived from Jatropha oil.

The laminate of the present invention can have various shapes such as a film shape, a sheet shape, a tube shape, a hose shape, a bottle shape, and a tank shape. The film shape, sheet shape, tube shape, and hose shape may be a corrugated shape or a convoluted shape.

A molded product formed from the laminate is also one aspect of the present invention. The molded article of the present invention has a high elastic modulus retention even at high temperatures. In addition, the molded article is excellent in fuel barrier properties and has mechanical strength, chemical resistance, oil resistance, heat resistance and flexibility.

The laminate of the present invention is a laminate having both chemical resistance, oil resistance, heat resistance, and cold resistance, and is useful as a member used in a fuel piping system, for example, a fuel tube or a fuel container. In particular, it is useful as a multilayer fuel tube or multilayer fuel container for automobile engines and peripheral devices, AT devices, fuel systems and peripheral devices. For example, fuel tubes for filler hose, evaporative hose, breather hose, etc. for automobiles; in-tank tubes arranged in fuel tanks; fuel containers for automobiles, fuel containers for motorcycles, fuel containers for small generators And a fuel container such as a lawn mower fuel container.

In addition, the laminated body is further used as an engine body of an automobile engine, a main motion system, a valve system, a lubricant / cooling system, a fuel system, an intake / exhaust system; a drive system transmission system; a chassis steering system; Brake system: Gaskets and non-contact types that require heat resistance, oil resistance, fuel oil resistance, antifreeze resistance for engine cooling, and steam resistance, such as basic electrical parts of control equipment, control system electrical parts, equipment electrical parts, etc. Sealing materials such as contact type packings (self-seal packing, piston ring, split ring type packing, mechanical seal, oil seal, etc.) are included.

The sealing material used for the engine body of the automobile engine is not particularly limited, but includes, for example, a cylinder head gasket, a cylinder head cover gasket, an oil pan packing, a gasket such as a general gasket, an O-ring, a packing, a timing belt cover gasket, and the like. For example, a sealing material.

The seal material used in the main motion system of the automobile engine is not particularly limited, and examples thereof include a shaft seal such as a crankshaft seal and a camshaft seal.

The seal material used in the valve system of an automobile engine is not particularly limited, and examples thereof include a valve stem oil seal for an engine valve.

There are no particular limitations on applications other than automotive applications,
Films, sheets; food films, food sheets, chemical films, chemical sheets, diaphragm pump diaphragms and various packing tubes, hoses; solvent tubes or solvent hoses, paint tubes or paint hoses, Automotive radiator hose, air conditioner hose, brake hose, wire covering material, food and beverage tube or food and beverage hose, underground underground tube or hose for gas station, subsea oil field tube or hose bottles, containers, tanks, etc. Tanks, paint tanks, chemical containers such as semiconductor chemical containers, food and drink tanks, etc .; various mechanical seals such as seals for hydraulic equipment, gears, etc. Among the above, it can be suitably used particularly for tubes or hoses. .

The tube or hose may have a corrugated region in the middle. Such a corrugated region is an appropriate region in the middle of the hose body formed into a corrugated shape, a corrugated shape, a convoluted shape, or the like.

Since the tube or hose has a region in which a plurality of folds of such corrugations are arranged in an annular shape, one side of the annular shape can be compressed in that region, and the other side can be expanded outward. It can be easily bent at any angle without stress fatigue or delamination.

The method for forming the corrugated region is not limited, but it can be easily formed by first forming a straight tube and then performing molding or the like to obtain a predetermined corrugated shape.

The laminated body of the present invention can be suitably used for applications where there is a portion that comes into contact with fuel when using a fuel hose (tube), a tank, or the like.

A fuel hose formed from the laminate is also one aspect of the present invention. Since the laminate of the present invention has a high elastic modulus retention even at high temperatures as described above, it is suitable for applications requiring high temperature resistance such as fuel piping, and for fuel hoses used for automobile fuel piping tubes. It can be suitably used as a laminate. In this case, the portion in contact with the fuel is preferably the layer (A). That is, the innermost layer is preferably the layer (A).

The innermost layer of the fuel hose is liable to accumulate an electrostatic charge due to contact with a flammable liquid such as gasoline, but the innermost layer preferably contains a conductive filler in order to avoid igniting by the electrostatic charge.

The conductive filler is not particularly limited, and examples thereof include conductive simple powders or conductive single fibers such as metals and carbons; powders of conductive compounds such as zinc oxide; surface conductive powders.

The conductive single powder or conductive single fiber is not particularly limited, and examples thereof include metal powders such as copper and nickel; metal fibers such as iron and stainless steel; carbon black, carbon nanotubes, carbon fibers, Japanese Patent Laid-Open No. 3-174018 Examples thereof include carbon fibrils described in publications and the like.

The surface conductive treatment powder is a powder obtained by conducting a conductive treatment on the surface of a nonconductive powder such as glass beads or titanium oxide. The method for conducting the conductive treatment is not particularly limited, and examples thereof include metal sputtering and electroless plating. Among the conductive fillers described above, carbon black is preferably used because it is advantageous in terms of economy and prevention of electrostatic charge accumulation.

An in-tank tube (first in-tank tube of the present invention) formed from the laminate of the present invention is also one aspect of the present invention.
Usually, a fuel piping system of an automobile sucks and supplies fuel (gasoline or the like) for operating an engine from a fuel tank. The fuel is sucked up by a fuel pump installed in the fuel tank. A hose connected to the fuel pump in the fuel tank is called an in-tank tube.

The in-tank tube is installed in the fuel tank. For example, FIG. 1 is a schematic view showing the inside of a fuel tank of an automobile. The in-tank tube 1 and the fuel pump 5 are usually connected by a connector 10. The press-fitting part of the connector 10 is connected to the in-tank tube 1 by press-fitting into the end part of the in-tank tube 1, and the engaging part of the connector is connected by engaging with the engaged part of the fuel pump 5. The Since the in-tank tube is installed in the fuel tank, a higher temperature resistance is required. Also, moderate hardness is required.
The laminate of the present invention is particularly suitable for an in-tank tube because it has an appropriate hardness and has a high elastic modulus retention even at high temperatures.

The diameter of the first in-tank tube of the present invention is usually set to an inner diameter of 5 to 20 mm, preferably 6 to 15 mm. The wall thickness is set to 0.5 to 5 mm, preferably 0.7 to 3 mm.

The second in-tank tube of the present invention includes a layer (A ′) made of a fluororesin, and the fluororesin is a copolymer containing a polymer unit based on tetrafluoroethylene and a polymer unit based on vinylidene fluoride. .
It is desirable that the in-tank tube has a high elastic modulus retention even at high temperatures and has an appropriate hardness. However, the second in-tank tube of the present invention has a layer made of the specific fluororesin. By containing, even at high temperatures, the elastic modulus retention rate is high, and it has an appropriate hardness.
The second in-tank tube of the present invention is usually disposed in the fuel tank.

As the fluororesin of the layer (A ′), the same fluororesin as that forming the fluororesin layer (A) can be suitably employed in the laminate of the present invention.

The second in-tank tube of the present invention may have a one-layer configuration consisting of only the layer (A ′) made of the fluororesin, or a two-layer configuration in which an arbitrary material is further laminated on the layer (A ′). It may be.
From the viewpoint of the elastic modulus retention at the time of high temperature use, the above one-layer configuration is preferable. That is, an in-tank tube made of only the layer (A ′) made of the fluororesin is also a preferred embodiment of the present invention.
From the viewpoint of cost, a structure having two or more layers is preferable. For example, it is a laminate of a layer (A ′) and a layer made of at least one resin selected from the group consisting of polyamide resin and polyethylene resin. Is preferred.
From the viewpoint of hardness, a laminate with the layer (B) described in the laminate of the present invention is preferable.
In the case where the second in-tank tube of the present invention has a configuration of two or more layers, for example, a two-layer configuration consisting of a layer (A ′) and a layer (B), between the same or different two types of layers (B) Examples include a three-layer configuration in which a layer (A ′) is inserted, and a three-layer configuration in which a layer (B) is inserted between two types of the same or different layers (A ′).

The diameter of the second in-tank tube of the present invention is usually set to an inner diameter of 5 to 20 mm, preferably 6 to 15 mm. The wall thickness is set to 0.5 to 5 mm, preferably 0.7 to 3 mm. When the second in-tank tube of the present invention has a single-layer configuration, the thickness of the layer (A ′) is the same as the above thickness, but from the viewpoint of hardness, the thickness of the layer (A ′) is 0.00. 8 mm or more is preferable, and 0.9 mm or more is more preferable.
When the 2nd in-tank tube of this invention is a structure of 2 or more layers, it is preferable that the thickness of a layer (A ') is 0.01-4 mm, and it is more preferable that it is 0.03-2 mm.

The second in-tank tube of the present invention can be produced by extrusion using an extruder or the like. In the case of two or more layers, the same manufacturing method as that of the above-described laminate of the present invention can be employed.

The 2nd in-tank tube of this invention can be used conveniently when using the biodiesel fuel from which use environment becomes high temperature. Biodiesel fuel refers to a fuel containing FAME obtained by subjecting vegetable oil to transesterification with methanol and decomposing and removing glycerin. Examples of FAME include RME derived from rapeseed oil, SME derived from soybean, SFME derived from sunflower oil, PME derived from palm oil, mixed fatty acid methyl ester containing unsaturated fatty acid methyl ester such as JME derived from Jatropha oil.

Hereinafter, the present invention will be described in more detail with reference to examples. Each physical property was measured by the following method.

Using fluorine resin monomer composition nuclear magnetic resonance apparatus AC300 (manufactured by Bruker-Biospin), the measurement temperature is (polymer melting point + 20) ° C., and ¹⁹ F-NMR measurement is performed. In some cases, the elemental analysis was appropriately combined.

Using a melting point differential scanning calorimeter RDC220 (manufactured by Seiko Instruments), heat measurement was performed at a heating rate of 10 ° C./min in accordance with ASTM D-4591, and the melting point was obtained from the peak of the obtained endothermic curve.

Melt flow rate [MFR]
MFR is based on ASTM D3307-01, and uses a melt indexer (manufactured by Toyo Seiki Co., Ltd.) at a mass of 297 ° C. under a 5 kg load from a nozzle having an inner diameter of 2 mm and a length of 8 mm per 10 minutes g / 10 min) was defined as MFR.

Thermal decomposition start temperature (1% mass loss temperature)
The thermal decomposition start temperature was defined as the temperature at which the mass of the fluororesin subjected to the heating test using a differential thermal / thermogravimetric measuring device [TG-DTA] decreased by 1 mass%.

It is a value measured at a tensile speed of 100 mm / min using a micro dumbbell having a thickness of 2 mm as described in tensile modulus ASTM D1708. The results are average values carried out with N = 5.

Storage modulus (E ')
The storage elastic modulus is a value measured at 170 ° C. by dynamic viscoelasticity measurement. More specifically, the length is 30 mm, the width is 5 mm, and the thickness is 0.25 mm with a dynamic viscoelastic device DVA220 manufactured by IT-Measurement Control Co., Ltd. Is a value measured under the conditions of tension mode, grip width 20 mm, measurement temperature 25 ° C. to 250 ° C., temperature rising rate 2 ° C./min, and frequency 1 Hz.

Synthesis example 1
Distilled water 900 L was charged into a 3000 L autoclave and sufficiently purged with nitrogen. Then, 674 kg of perfluorocyclobutane was charged, and the temperature in the system was maintained at 35 ° C. and a stirring speed of 200 rpm. Subsequently, 207 g of CH ₂ = CHCF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF _3, 62.0 kg of tetrafluoroethylene (TFE) and 18.1 kg of vinylidene fluoride (VDF) were sequentially charged, and then the polymerization initiator di-n Polymerization was initiated by adding 2.24 kg of a 50 mass% methanol solution of propylperoxydicarbonate [NPP]. Simultaneously with the start of polymerization, 2.24 kg of ethyl acetate was charged. Since the system pressure decreases as the polymerization proceeds, a TFE / VDF mixed gas monomer (TFE / VDF: 60.2 / 39.8 (mol%)) is charged, and CH _{2 is} added to 100 parts of the added mixed gas. = CHCF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF ₃ was simultaneously charged so as to be 1.21 parts, and the system internal pressure was kept at 0.8 MPa. When the additional charge of the mixed gas monomer finally reached 110 kg, the polymerization was stopped, the pressure was released and the pressure was returned to atmospheric pressure, and then the obtained TFE / VDF / CH ₂ = CHCF ₂ CF ₂ CF ₂ CF _{2 was obtained.} The CF ₂ CF ₃ copolymer (fluororesin 1) was contacted with 0.8 mass% ammonia water at 80 ° C. for 1 hour, washed with water and dried to obtain 102 kg of powder.

Next, melt extrusion was performed at a cylinder temperature of 290 ° C. using a φ50 mm single screw extruder to obtain pellets. Subsequently, the obtained pellet was heated and deaerated at 170 ° C. for 10 hours.

The obtained pellets had the following composition and physical properties.
_{TFE / VDF / CH 2 = CHCF} 2 CF 2 CF 2 CF 2 CF 2 CF 3 = 60.1 / 39.6 / 0.3 ( mol%)
Melting point: 218 ° C
MFR: 1.7 g / 10 min (297 ° C.-5 kg)
Thermal decomposition start temperature (1% mass loss temperature): 388 ° C.
Tensile modulus: 421 MPa (room temperature), 133 MPa (100 ° C.), 111 MPa (150 ° C.)
Storage elastic modulus (E ′): 130 MPa

Reference example 1
The tensile elastic modulus was measured by the above-mentioned method for a fluororesin (PVDF: Solef 60512, manufactured by SOLVAY SOLEXIS). The results are shown in Table 1 below together with the results of the fluororesin 1.

Example 1
Using a four-type four-layer tube extrusion device equipped with a multi-manifold die, the outer layer of the tube is nylon 610 (manufactured by Daicel-Evonik, melting point: 215 ° C.), and the inner layer is the fluororesin 1 polymerized in Synthesis Example 1. Thus, nylon 610 was supplied to the outer layer and outermost layer extruder, and fluororesin was supplied to the inner layer and innermost layer extruder to form a two-layer tube having an outer diameter of 8 mm and an inner diameter of 6 mm. The die temperature of the extruder was set at 280 ° C., and the tube take-up speed was set at 8.0 m / min. The thickness of the inner layer fluororesin was 0.5 mm, and the thickness of the outer layer polyamide resin (nylon 610) was 0.5 mm. The adhesive strength was 2.5 N / cm. Even when the prepared tube was attached to the fuel pump and a pressure of 1 MPa was applied at 130 ° C., the fuel did not leak from the tube fastening portion.

Example 2
The fluororesin 1 polymerized in Synthesis Example 1 was supplied to a single-layer tube extruder to form a single-layer tube having an outer diameter of 8 mm, an inner diameter of 6 mm, and a layer thickness of 1 mm. The die temperature of the extruder was set at 280 ° C., and the tube take-up speed was set at 8.0 m / min. Even when the prepared tube was attached to the fuel pump and a pressure of 1 MPa was applied at 130 ° C., the fuel did not leak from the tube fastening portion.

Comparative Example 1
Using a four-kind, four-layer tube extruder equipped with a multi-manifold die, nylon 610 is placed on the outer layer and outermost layer extruders so that the outer layer of the tube is nylon 610 and the inner layer is fluororesin (PVDF: Solef 60512). Then, PVDF was supplied to the inner layer and innermost layer extruder to form a tube having an outer diameter of 8 mm and an inner diameter of 6 mm. The die temperature of the extruder was set to 250 ° C., and the tube take-up speed was set to 8.0 m / min. The thickness of the inner layer fluororesin was 0.5 mm, and the thickness of the outer layer polyamide resin (nylon 610) was 0.5 mm. The adhesive strength was 1 N / cm or less. When the prepared tube was attached to a fuel pump and a pressure of 1 MPa was applied at 130 ° C., the fuel leaked from the tube fastening portion and could not be used.

Since the laminate of the present invention has a high elastic modulus retention even at high temperatures, it is useful as a fuel peripheral member such as a fuel piping system of an automobile, and can be suitably used as, for example, an in-tank tube.

1, 1 ': Inn tank tube 2: Fuel tank 3: Fuel 4: Filter 5: Fuel pump 6: Jet pump 7: Housing 8: Spring 10: Connector

Claims (11)

A laminate comprising a layer (A) made of a fluororesin and a layer (B) made of a polyamide resin,
The fluororesin is a copolymer containing a copolymerized unit of tetrafluoroethylene and a copolymerized unit of vinylidene fluoride, and a storage elastic modulus (E ′) at 170 ° C. by dynamic viscoelasticity measurement is 60 to 400 MPa. A laminate characterized by the above. The fluororesin comprises tetrafluoroethylene, vinylidene fluoride, an ethylenically unsaturated monomer represented by the formula (1) and / or an ethylenically unsaturated monomer represented by the formula (2). The laminate according to claim 1, wherein the laminate comprises a copolymer unit.
Formula (1): CX ¹ X ² = CX ³ (CF ₂ ) _n X ⁴
(Wherein X ¹ , X ² , X ³ and X ⁴ are the same or different and represent H, F or Cl, and n represents an integer of 0 to 8, except for tetrafluoroethylene and vinylidene fluoride. )
Formula (2): CF ₂ = CF-ORf ¹
(In the formula, Rf ¹ represents an alkyl group having 1 to 3 carbon atoms or a fluoroalkyl group.) The laminate according to claim 1, wherein the polyamide resin has a melting point of 200 ° C. or higher. A molded article formed from the laminate according to claim 1, 2 or 3. An in-tank tube formed from the laminate according to claim 1, 2 or 3. The in-tank tube according to claim 5 disposed in the fuel tank. An in-tank tube including a layer (A ′) made of a fluororesin,
The fluororesin is a copolymer including a polymer unit based on tetrafluoroethylene and a polymer unit based on vinylidene fluoride, and a storage elastic modulus (E ′) at 170 ° C. by dynamic viscoelasticity measurement is 60 to 400 MPa. An in-tank tube characterized by The in-tank tube according to claim 7, comprising only a layer (A ') made of a fluororesin. The fluororesin comprises tetrafluoroethylene, vinylidene fluoride, an ethylenically unsaturated monomer represented by the formula (1) and / or an ethylenically unsaturated monomer represented by the formula (2). The in-tank tube according to claim 7 or 8, which is a copolymer containing copolymerized units.
Formula (1): CX ¹ X ² = CX ³ (CF ₂ ) _n X ⁴
(Wherein X ¹ , X ² , X ³ and X ⁴ are the same or different and represent H, F or Cl, and n represents an integer of 0 to 8, except for tetrafluoroethylene and vinylidene fluoride. )
Formula (2): CF ₂ = CF-ORf ¹
(In the formula, Rf ¹ represents an alkyl group having 1 to 3 carbon atoms or a fluoroalkyl group.) The in-tank tube according to claim 7, 8 or 9, wherein the fluororesin has a tensile elastic modulus at 150 ° C of 15% or more as compared with a tensile elastic modulus at room temperature. The in-tank tube according to claim 7, 8, 9 or 10, which is disposed in the fuel tank.

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